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Kinetic study of the reactions of NO3 with 3=chloropropene,

3-bromopropene and 3-iodopropene using LIF detection

E. Martinez:" B. Cabaiias," A. Aranda," P. Martin" and R. P. Wayneb

a Facultad de Quimicas, Universidad de Castilla-La Mancha, Campus Universitario sln, 13071,
Ciudad Real, Spain
Physical and Theoretical Chemistry Laboratory, University of Oxford, South Parks Road,
Oxford, U K OX1 3QZ
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The kinetics of the reactions of the nitrate radical, NO,, with 3-chloropropene and 3-bromopropene have been studied in the
temperature range 296-428 K, using the discharge-flow technique coupled to detection of NO, by laser-induced fluorescence. The
results obtained for the room-temperature rate constants are (0.49 0.02) x and (0.38 f 0.02) x cm3 molecule-'
s-', respectively, and the proposed Arrhenius expressions are k = (1.92 f 0.79) x lo-'' exp[(-2480 & 143/T)] and
k = (1.27 & 0.37) x lo-', exp[(- 1737 f 104)/T] cm3 molecule-' s-', respectively (errors quoted as a).
The study of the reaction between the NO, radical and 3-iodopropene has also been attempted using the same conditions. The
decomposition of 3-iodopropene with increasing temperature and the occurrence of some radical-radical reactions makes it
difficult to establish the Arrhenius parameters. A room-temperature rate constant of k < 3.91 f 0.02 x cm3 molecule-'
s - has been estimated.
An estimate of the corresponding rate coefficients for the reactions of these halopropenes with the OH radical has been made.
Tropospheric half-lives are calculated at night and during the day for typical NO, and OH concentrations, and show that both
radicals provide an effective tropospheric sink for these compounds.

The nitrate radical is an important intermediate in tropo-
spheric chemistry. Many reactions with organic and inorganic
compounds have been investigated.'-, Through these studies,
it has been shown that unsaturated hydrocarbons are highly
reactive towards the NO, radical, which may be an important
night-time sink for such chemicals. A knowledge of the rate
constants for reaction of NO, with unsaturated aliphatic con-
taminants in air is required to estimate the persistence, fate
and harmful effects of these toxic organic compounds. In this
context, the effects of ally1 chloride on the environment have
been widely d e ~ c r i b e d . ~ - ~
Early attempts to explain the reactivity of NO, towards
chlorinated alkenes were unsuccessful because of the substan-
tial scatter in the experimental r e ~ u l t s ,and
~ several different
structure-reactivity relationships were proposed for the reac-
tions with the hydroxyl radical and chlorine atoms. More
recently, further studies of the reactions of NO, with haloalk-
enes have been carried out8-" in an attempt to establish the
reactivity of these compounds towards the nitrate radical. In
this work, we report experimental kinetic results for the reac-
tions :
NO, + ClCH,-CH=CH, -+ products
NO, + BrCH,-CH=CH, -+ products
NO, + ICH,-CH=CH, -+ products (3)
in the gas phase over the temperature range 296-428 K.
In the atmosphere, the main loss processes for organic
species are photolysis and reactions with the O H radical and
the nitrate radical. For 3-chloropropene and 3-bromopropene,
which do not absorb actinic radiation (i.e. at wavelengths
2290 nm), the available kinetic data for other alkenes and
haloalkenes indicate that the reactions with OH and NO, are
expected to be the dominant atmospheric loss pathways. In
the case of 3-iodopropene, which undergoes photodissociation
on exposure to visible radiation, its reactions with tropo-
spheric radicals are expected to be relatively less important in
determining the atmospheric lifetime.
The reactivity of 3-chloropropene towards hydroxyl
radicalsI2 and NO, has been studied previously at room
temperature. The present study is the first investigation of
reactions (2) and (3), and the first study of the influence of
temperature on reactions (l), (2) and (3). Most kinetic work on
the reactions of NO, with haloalkenes involve chlorosubsti-
tuted alkenes. Only two studies are a~ailable'9'~in which
bromine or iodine atoms are present in the organic chain. Our
study should thus contribute to the clarification of the influ-
ence of the different substituent halogen atoms on the reacti-
vity.
Experimental
Details of the apparatus and experimental procedure have
'
been described previously,' and therefore only a brief
description is given here. All measurements of second-order
rate constants, k, were carried out in a fast-flow apparatus
under pseudo-first-order conditions in NO, .
A 115 cm long flow tube with an i.d. of 40 mm was used,
and the temperature was set between 296 and 428 K. Nitrate
(1) radicals, which are added to the flow tube through a fixed
(2) port, were generated by reaction of nitric acid vapour with
fluorine atoms from a microwave discharge passed through
5% F,-He mixtures. NO, concentrations in the range
(0.6-1.6) x lo1, molecule cm-' were used. Haloalkenes
were added through a sliding injector of 0.8 cm od with a
spray-nozzle tip. All halopropene concentrations gave
[reactant]/[NO,] ratios between 50 and 1000. Variation in
reaction time was achieved by changing the distance between
the injector and the detection cell.
Quantitative detection of NO, was carried out by monitor-
ing the fluorescence emitted after exciting the (0-0) 2E' t ,A2'
transition of NO,, pumping with R = 662.0 nm radiation
from a dye laser. Long-pass filters with a R = 665 nm cut off
were used as most of the fluorescence intensity lies at wave-
lengths > 710 nm.

J . Chem. SOC.,Faraday Trans., 1996,92(22),4385-4389 4385

 View Article Online

The laser system consisted of a dye laser pumped by the

second harmonic of an Nd/YAG laser (Scanmate 2C, Lambda
Physik). DCM dissolved in methanol was used as the dye
'1
solution. 2-5 mJ pulses of 0.105 cm-I bandwidth and 8 ns
duration were used to excite fluorescence which, for these
-
-+lS
0-
-
experimental conditions, was a linear function of laser power z

: :
-
\
and NO, concentration with zero intercepts. The detector was W0 1
VI
an R928 Hamamatsu photomultiplier tube and signal averag-
ing was achieved by a boxcar integrator (Standford RS 250)
capturing 100-300 fluorescence decays.
The sources of the halopropene used and their stated
=
?5 0.5
0
W -
purities were: 3-chloropropene (Jansen 99"/), 3-bromo-
propene (Jansen 990/,) and 3-iodopropene (Aldrich 98%). All
0 ~ 1 l l l ( l r r l l l 1 1 1 ( 1 1 1 l l l l l l l l l 1 l )
the reactants were purified by successive trap-to-trap distilla-
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0 0.01 0.02 0.03 0.04 0.05 0.06

.,
tions. In the case of 3-iodopropene, special measures were timels
taken to avoid its exposure to light as it decomposes giving
molecular iodine. Nitric acid vapour was obtained by bub- Fig. 1 First-order plots for the reaction of NO, with 3-
bling He through a 2 : 1 sulfuric acid-nitric acid mixture (P.A. chloropropene at 428 K. 0 , [3-chloropropene] = 1.49 x 1014 mol-
ecule cmW3; [3-chloropropene] = 2.08 x l O I 4 molecule ~ m - 0,
~ ;
Panreac). Molecular fluorine mixed with helium (5% F,-95% [3-chloropropene] = 2.82 x 1014 molecule A, [3-chloropro-
He) was supplied by Praxain and Union Carbide. pene] = 3.37 x loi4 molecule ~ m - ~ ; [3-chloropropene] +,
= 3.28 x 1014 molecule A, [3-chloropropene] = 4.69 x 1014
molecule ~ m - 0,
~ ;[3-chloropropene] = 6.28 x 1014molecule cm-3.

Results and Discussion

Decays of NO, concentration were obtained as a function of
time, and the logarithms of the ratios of the fluorescence
intensities in the absence and presence of reactants were
plotted for different contact times, in accordance with the
equation,
parameters were calculated from linear least-squares regres-
sion (Table 1). The measured activation energies for the reac-
tions of NO, with 3-chloropropene and 3-bromopropene
E, = 20.6 1.2 and 14.6 0.7 kJ mol-l, respectively, are of

ln([NO,],/[NO,],) = k[halopropene]t = k, t (I) T=298 K

40 y
I 7-1391 K
where k, is a pseudo-first order rate constant. 35 :
For reactions (1) and (2), straight lines were obtained for all T-428 K
these pseudo-first order plots for every halopropene concen- 30 A T-347 K
tration, and at all temperatures, which is consistent with the
model of elementary gas-phase reaction considered. Fig. 1
shows some typical plots obtained for reaction (1) at 428 K.
The slope of such plots yields the pseudo-first order rate con-
stant. 15 :
The rate constants obtained for reactions (1) and (2) at dif-
10 7
ferent temperatures are listed in Table 1. Plots of k, us. [3-
chloropropene] and C3-bromopropenel were linear with inter- 5 :
cepts close to zero at all the temperatures studied, so that no
evidence of secondary reactions was observed. The data
obtained for reaction (1) are displayed in Fig. 2. 0 2 4 6 8 1 0 1 2 1 4
The temperature dependence of the second-order rate con- [3-chloropropene]/lo'' molecule c m 3
stants was sought in Arrhenius plots (Fig. 3). Linear behaviour Fig. 2 Second-order plots for the reaction of NO, with 3-
was observed for both reactions (1) and (2), and the Arrhenius chloropropene at different temperatures

Table 1 Summary of the measured rate constants

T/K k/iO-I4 cm3 molecule-' s-l [reactant] / 1O molecule cm - EJkJ mol - ' A/10-I2 cm3 molecule-' s-'

3-chloropropene
298 0.49 0.02 2.5-13.9
348 1.41 f 0.10 2.1-10.5 20.6 f 1.2 19.2 i-7.9
391 3.16 f 0.13 1.4-7.0
428 6.41 f 0.46 1.3-6.3
3-bromopropene
297 0.35 & 0.02 1.2-4.7
346 0.80 f 0.05 0.8-3.6 14.6 f 0.7 1.27 f 0.37
39 1 1.41 f 0.13 0.6-3.8
428 2.37 f 0.14 0.7-3.9
3-iodopropene
296 G3.91 f 0.23 0.6-2.6
346 G5.75 0.55 0.4-2.3
39 1 G8.20 f 1.14 0.7-2.2
427 G9.97 & 0.36 0.3-1.9
~ ~ ~ ~~~~~

WO,] = (0.6 f 1.8) x 10" molecule PT = 1.1 & 1.3 Torr. Errors quoted are f a .

4386 J . Chem. SOC.,Faraday Trans., 1996, Vol. 92

 View Article Online

3chloropropene

.
A T=427 K

-30 7 30 - T-296 K

-
n
I
In
3-bromopropene

25 7
T=346 K

7a3 -31
- -
-u
3
Q
0
- 20

2 -32
v1
\
*- 15 -
5
*
\
W 10
-c -33

1
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-34 0 - 1
2 2.5 3 3.5 0 5 10 15 20 25
[3-iodopropene] / 10 13molecule
Fig. 3 Arrhenius plots for the reaction of NO, with 3-chloropropene Fig. 4 Second-order plots for the reaction of NO, with 3-iodo-
and 3-bromopropene in the temperature range 296-428 K propene at different temperature

the same order of magnitude as for other reactions of NO,

with alkenes.
According to these experimental results, we propose the
expressions :
k, = (1.92 & 0.79) x lo-'' exp[(-2480 f 143/T)]
(cm3 molecule-' s-')
k, = (1.27 & 0.37) x lo-', exp[(-1737 f 104/T)]
(cm3 molecule-' s-l)
to predict rate constants of reactions (1) and (2) in the range of
temperature 296-428 K.
In the reaction of the nitrate radical with 3-iodopropene,
semilogarithmic NO, concentration decay plots were also
linear, with intercepts close to zero at all temperatures [as for
reactions (1) and (2)]. When plotting the experimental pseudo-
first-order rate constants k, against 3-iodopropene concentra-
tions, straight lines were obtained but the intercepts were
significant, and rose with temperature (Fig. 4).Our experimen-
tal technique, which normalises to [NO,l0 at each injector
position, would usually be expected not to give an intercept.
The existence of this intercept thus suggests an additional loss
process of NO,, dependent on the pressure of 3-iodopropene.
We attribute this loss to the decomposition of a small amount
of 3-iodopropene when it is heated inside the flow tube,
because molecular iodine was observed in the cooled trap,
downstream from the reaction vessel. Ally1 radicals and iodine
atoms must therefore be generated. Both are expected to react
rapidly with the NO, radical and to initiate a complex reac-
tion sequence that is, as yet, only partially characterised.'
These secondary reactions may generate other species such as
I 0 and CH,=CHCH,O, which would consume further NO,.
Thus, although the rate constants extracted from plots in Fig.
4 and summarized in Table 1, do follow Arrhenius behaviour,
yielding an apparent activation energy of 7.58 & 0.36 kJ
mol-' typical of additions of NO, to alkenes, it is not pos-
sible to assert that these rate coefficients are due exclusively to
the elementary reaction between 3-iodopropene and the
nitrate radical, and they should be considered as upper limits.
This work is the first investigation of the temperature
dependence of the kinetics of the reactions of NO, with 3-
chloropropene, 3-bromopropene and 3-iodopropene. Tuazon
(11) et a!." studied the reaction of 3-chloropropene with OH rad-
icals and ozone at room temperature, and there is also a pre-
vious relative-rate study of reaction (1) at room temperature',
in which a rate constant k = 5.35 x cm3 molecule-'
(111) s- ' was estimated, quite different from the value obtained in
the present work.
In any case, Atkinson,' does not recommend the previous
results from his group as he believes that they could be subject
to significant uncertainties. No data for reactions (2) and (3)
have been found, so that no comparison may be established,
but the results obtained for room-temperature rate constants
and Arrhenius parameters show that the behaviour is similar
to those of other reactions of NO, with alkenes and haloalk-
enes.'
From the experimental rate constants measured in this
work, it is possible to estimate the room-temperature rate
coefficients for the reactions of 3-chloropropene, 3-
bromopropene and 3-iodopropene with the OH radical, since
reactions (l), (2) and (3) seem to proceed through a mechanism
similar to that for other alkenes.'-'' The correlation between
the reactivity toward alkenes of O H and NO, radical found
by Wayne et al.'
log kNO3= 21.6 + 3.32 log ko, (IV)
can then be used to yield the calculated values for k,, that are
shown in Table 2.
The agreement found in the case of 3-chloropropene
between the predicted k,, and that measured experimentally
is quite good. As no experimental data for reactions of O H
with 3-bromopropene and 3-iodopropene have been reported
yet, the estimated values presented in this work can be used as
a first approximation to the reaction rate constant.

Table 2 Tropospheric half-lives of 3-chloropropene, 3-bromopropene and 3-iodopropene estimated from the room temperature rate constant for
reaction with NO, during the night and for reaction with OH during the day

kN03a/1~-14
cm3 kOHb/1O-" cm3 k, '/I 0- ' cm
compound molecule- s - ' molecule - ' s - molecule - s - TnighJh h,/h
~~ ~~ ~~

3-chloropropene 0.495 f 0.025 +

1.53 0.20 1.7 0.5 38.9 f 2.0 11.3 f 3.3
3-bromopropene 0.385 k 0.025 1.41 f 0.30 - 50.0 i-3.2 13.7 f 2.9
3-iodopropene G3.91 f 0.23 G2.85 f 0.05 - 34.9 f 0.3 36.8 0.1

a Experimental (this work). ' Calculated, see text. Experimental (ref. 12). Errors quoted are f6.

J . Chem. SOC., Faraday Trans., 1996, Vol. 92 4387


Aird et aL8 made a first attempt to carry out a structure-
reactivity analysis of the reactions- of the nitrate radical, and a
reactivity factor for -CH,Cl of 0.52 0.12 was proposed. It
was shown that a much larger kinetic data base was still
required to establish a reliable set of rate constants for basic
structures and group factors. Using our experimental results,
it is possible to estimate the group reactivity factors of
-CH,Br and -CH,I when they are attached to the double
bond as 0.40 _+ 0.09 for the former and 4.12 & 0.94 for
-CH,I as an upper limit, although more experimental data
are still required to extract more reliable factors.
The reactivity of NO, towards alkenes and halogenoalk-
enes has recently been to be dependent on the ion-
ization potentials, Ei of the unsaturated reactants estimated
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from the energy of the highest occupied molecular orbital
(HOMO). The energies of the HOMOS have been obtained
for 3-chloropropene (- 10.22 eV), 3-bromopropene (- 10.46
eV) and 3-iodopropene (- 9.44 eV) by means of semiempirical
calculations carried out with the Hyperchem 3.0 package and
PM3 parametrization. A correlation has been proposed for
simple alkenes and alkenes that are not halosubstituted in the
double b ~ n d ~ ? ~ ? "
-log(k,,,/cm3 molecule-1 s-l) = 3.276EJeV - 19.38 (V)
The rate constants obtained for the reactions of NO, with
3-chloropropene and 3-bromopropene fit eqn. (V) quite well.
Thus, the present work, together with our previous study of
the reactions of the nitrate radical with 1,l-dichloropropene,
(E)-1,3-dichloropropene and 2,3-di~hloropropene,~tends to
confirm that the alkenes with halogen atoms attached to the
double bond present reactivities quite different from those
alkenes with the halogen atom joined to other positions, as
had been observed p r e v i o ~ s l y . ~
In, ~the case of species like
3-chloropropene and 3-bromopropene, the behaviour with
respect to the ionization potential is similar to that of simple
alkenes.
As the room-temperature rate constant for reaction of 3-
iodopropene with NO, falls far from the regression line, the
contribution of the atomic orbitals to the HOMO was also
explored. It was noticed that the HOMO was mainly localised
on the iodine atom of the 3-iodopropene molecule, while in
the other alkenes it was on the carbon atoms where the
double bond formally resides. This observation can explain
why the HOMO energy might be of the wrong magnitude in
this case.
The anomalous kinetic results for 3-iodopropene may also
arise because the elementary reaction with NO, has not been
unequivocally characterised (see earlier discussion of possible
secondary processes). Further, although PM3 is parametrized
for iodine atoms, the validity of the calculation in molecules
with such large atoms is not well checked yet.
The reactions of NO, radicals with alkenes proceed via
electrophilic addition of the radical to the double bond to
form an excited radical adduct. Under atmospheric condi-
tions, this irreversible step is followed by the addition of 0, to
give nitrooxyalkylperoxy radicals.' At low pressure and in the
4388 J . Chem. SOC.,Faraday Trans., 1996, Vol. 92
View Article Online
absence of 02,it has been proposed that the primary excited
adduct decomposes to an epoxide and NO,. Although recent
evidence16.' shows that this pathway can sometimes account
for 17% of the products under atmospheric conditions, it has
generally been neglected in high-pressure experiments, as
increased total pressure and 0, partial pressure decrease the
yield of epoxide and NO,.
The nitrooxyalkylperoxy radicals subsequently yield nitro-
oxyalkoxy radicals through reactions with NO, NO, and
HO, .l The nitrooxyalkoxy radicals can participate in differ-
ent reaction sequences but, as suggested by the results of
Wangberg et a1.,'* who studied the products of the reactions
of NO, and different halobutenes, the presence of H atoms
attached to the alkoxy-carbon, and a low level of substitution
in the structure of the alkenes, would enhance the reaction
with 0, to form HO, and halo-substituted aldehydes or
ketonitrates. In accordance with these ideas, we propose the
mechanism shown in Scheme 1 for reactions of 3-
chloropropene, 3-bromopropene and 3-iodopropene initiated
by attack of NO, under atmospheric conditions. These reac-
tions are thus a potential source of OH in the dark, and con-
sequently of H,O, . Daytime photolysis is expected to be the
main loss process for ketonitrates in the atmosphere."
With regard to the atmospheric implications of the reac-
tions studied here, it is possible to estimate the lifetime
at night of 3-chloropropene, 3-bromopropene and 3-
iodopropene in the troposphere, assuming the reactions with
nitrate radicals to be the dominant loss processes. The night-
time half-lives, defined as ln2/(k[halopropene]), are given in
Table 2, calculated on the basis of an average concentration of
NO, during the night of lo9 molecule cm-,.l
Assuming that sinks other than the reaction with OH rad-
icals during the day can be neglected, it is possible to calculate
the daytime half-lives using the rate constants estimated in
this work for the reactions of OH and 3-iodopropene, 3-
bromopropene and 3-chloropropene (experimental value,
Table 2).
For both night- and day-time, it may be seen that the reac-
tions of the halopropenes with NO, and OH radicals are fast,
showing that these tropospheric processes provide effective
loss pathways for such compounds.
Conclusion
The kinetics of the reactions of 3-chloropropene, 3-
bromopropene and 3-iodopropene with NO, have been fol-
lowed in the temperature range 296-428 K.
The rate coefficients measured at room temperature show
that these reactions may be of tropospheric relevance, as is
also expected for the corresponding reactions with OH rad-
icals.
Our recent work on the reactions between dichloro-
propenes and NO, l 1 and the present study show the rele-
vance of LIF as a quite selective and sensitive technique to
follow the reaction of the nitrate radical.
The decomposition of 3-iodopropene when heated produces

a complex system of radical-radical reactions that are difficult
to characterise. Although this effect is expected to be less
important at room temperature, the corresponding rate coefi-
cient does not fit the correlation with ionization potential that
is found for other alkenes of similar structures. Further inves-
tigation of the reaction between NO, and 3-iodopropene is
thus required to confirm the room-temperature kinetic con-
stant and to verify the Arrhenius parameters.
We wish to thank Dr. C. E. Canosa-Mas for helpful dis-
cussions on some points in this paper.
References
Published on 01 January 1996. Downloaded by University of Birmingham on 30/10/2014 12:26:30.
R. P. Wayne, I. Barnes, P. Biggs, J. Burrows, C. E. Canosa-Mas,
J. Hjorth, G. Le Bras, G. Moortgat, D. Perner, G. Poulet, G.
Restelli and H. Sidebottom, Atmos. Enuiron. Part A , 1991,25, 1.
R. Atkinson, J . Phys. Chem. Re$ Data, 1991,20,459.
U. Platt and F. Heintz, Isr. J . Chem., 1994,34,289.
K. Hooper, K. J. Ladou, J. S. Rosembaum and S . A. Book, Am. J .
Ind. Med., 1992,22,793.
H. Verhaar, C. Van Leeuen and J. Hermens, Chemosphere, 1992,
25,471.
J. Freeman, J. Johnson, R. Yost and D. Kuehl, Anal. Chem., 1994,
66,1902.
D. Grosjean and E. L. Williams, Atmos. Enuiron. Part A , 1992,
26, 1405.
View Article Online
8 W. S . Aird, C. E. Canosa-Mas, D. J. Cook, G. Marston, P. S .
Monks, R. P. Wayne and E. Ljungstrom, J . Chem. SOC.,Faraday
Trans., 1992,88, 1093.
9 G. Marston, P. S . Monks, C. E. Canosa-Mas and R. P. Wayne, J .
Chem. SOC.,Faruday Trans., 1993,89,3899.
10 B. Cabafias, G. Marston and R. P. Wayne, J . Chem. SOC.,
Faraday Trans., 1995,91,1185.
11 E. Martinez, B. Cabaiias, A. Aranda and R. P. Wayne, J . Chem.
SOC.,Faraday Trans., 1996,92,53.
12 E. C. Tuazon, R. Atkinson and S . M. Aschmann, Int. J . Chem.
Kinet., 1990,22,981.
13 R. Atkinson, S. M. Aschamann and M. A. Goodman, Int. J .
Chem., 1987,19,299.
14 P. Carlier, H. Hannachi, A. Kartoudis, A. Martinez and G.
Mouvier, Air Pollution Report 9. EUR.11440. Tropospheric N O ,
Chemistry, Gas Phase and Multiphase Aspects, 1987, p. 133.
13 R. M. Chambers, A. C . Heard and R. P. Wayne, J . Phys. Chem.,
1992,96,3321.
16 H. Skov, Th. Benter, R. Schinder, J. Hjorth and G. Restelli,
Atmos. Enuiron., 1994,28, 1583.
17 M. Olzmann, Th. Benter, M. Liesner and R. N. Schlinder, Atmos.
Environ., 1994,28, 2677.
18 I. Wangberg, E. Ljungstrom, J. Hjorth and G. Ottobrini G, J .
Phys. Chem., 1990,94, 8036.
19 I. Barnes, K. Becker and T. Zhu, J . Phys. Chem., 1990,94,2413.
Paper 6/01359G; Received 26th February, 1996
J . Chem. SOC.,Faraday Trans., 1996, Vol. 92 4389